KR101305716B1 - Eco flooring material using polylactic acid resin with excellent plasticity - Google Patents

Abstract

Disclosed is an eco-friendly PLA flooring material having excellent plasticity that can realize an eco-friendly flooring material using a PLA (poly lactic acid) resin and an eco-friendly plasticizer.
Eco-friendly PLA flooring material excellent in plasticity according to the present invention is a flooring material formed of one or more layers, at least one layer of the flooring material comprises a PLA (poly lactic acid) resin and non-phthalate-based plasticizer, the non-phthalate-based The plasticizer includes at least one of citric acid ester or acetyl citric acid ester, and the ester is composed of one citric acid molecule and three alcohol molecules arbitrarily selected and combined from ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol and octyl alcohol. It is characterized by.

Description

Eco-friendly PLA Flooring with Excellent Plasticity {ECO FLOORING MATERIAL USING POLYLACTIC ACID RESIN WITH EXCELLENT PLASTICITY}

The present invention relates to a flooring having a laminated structure, and more particularly, to apply a PLA (polylactic acid) resin obtained from a plant resource to at least one layer constituting the flooring, and to apply an environmentally friendly plasticizer (plasticizer) The present invention relates to a technology capable of manufacturing eco-friendly PLA flooring having excellent plasticity.

Floor materials used in buildings such as houses, mansions, apartments, offices or shops are mainly based on petroleum resin such as polyvinyl chloride (PVC).

The flooring material using said polyvinyl chloride etc. is manufactured by extrusion or a calendering method etc. using resin, such as polyvinyl chloride (PVC). However, since the raw material of the polyvinyl chloride resin is based on petroleum resources, there may be a big problem in the supply and demand of raw materials in the future due to exhaustion of petroleum resources.

In addition, polyvinyl chloride (PVC) flooring is required to be used in terms of environmental friendliness due to the generation of many harmful substances at the time of use or disposal.

On the other hand, in the case of plasticizers, phthalate-based plasticizers have been used in the past. However, phthalate-based plasticizers may be harmful to humans due to toxicity, and thus are subject to regulation.

An object of the present invention is to provide an eco-friendly PLA flooring material having excellent plasticity by constructing a flooring material, at least one layer using a PLA resin and also applying a non-phthalate-based plasticizer as a plasticizer.

Eco-friendly PLA flooring material having excellent plasticity according to an embodiment of the present invention for achieving the above object is formed in at least one layer, at least one layer of the flooring is a PLA (poly lactic acid) resin and non-phthalate-based Eco-friendly plasticizer, the non-phthalate plasticizer comprises at least one of citric acid ester or acetyl citric acid ester, the ester is selected from one citric acid molecule and ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol It is characterized by consisting of three alcohol molecules are combined.

Eco-friendly PLA flooring material having excellent plasticity according to another embodiment of the present invention for achieving the above object in the flooring comprising a chip through layer (Chip Through layer), the chip through layer is PLA resin and non-phthalate-based eco-friendly plasticizer The non-phthalate plasticizer comprises at least one of citric acid ester or acetyl citric acid ester, wherein the ester is one citric acid molecule and optionally selected from ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol It is characterized by consisting of three alcohol molecules.

Eco-friendly PLA flooring material having excellent plasticity according to another embodiment of the present invention for achieving the above object, in the flooring comprising a chip inlaid layer (chip inlaid layer), glass fiber impregnation layer and the back layer, the At least one of the chip inlay layer and the back layer comprises a PLA resin and non-phthalate-based eco-friendly plasticizer, the non-phthalate-based plasticizer comprises at least one of citric acid ester or acetyl citric acid ester, the ester is one citric acid The molecule is composed of three alcohol molecules which are arbitrarily selected and combined from ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol and octyl alcohol.

The eco-friendly PLA flooring material having excellent plasticity according to the present invention has an advantage of realizing an eco-friendly flooring material having excellent plasticity by using a PLA (poly lactic acid) resin based on plant resources and adding an eco-friendly plasticizer.

In addition, the eco-friendly PLA flooring material having excellent plasticity according to the present invention has the advantage of increasing the texture effect of natural wood by adding wood powder, rosin and the like.

Figure 1 shows an example of a general laminated flooring that can be applied to the present invention.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail with the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but is capable of many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

Hereinafter, with reference to the accompanying drawings will be described in detail with respect to the eco-friendly PLA flooring material having excellent plasticity according to the present invention.

Figure 1 shows an example of a general laminated flooring that can be applied to the present invention, it shows an example consisting of a surface treatment layer 110, a transparent layer 120, a printed layer 130 and the back layer 140 from above.

Eco-friendly PLA flooring material having excellent plasticity according to an embodiment of the present invention may be formed of one layer or a plurality of layers as shown in FIG.

At this time, the at least one layer constituting the flooring is using a polylactic acid (PLA) resin, and also an eco-friendly plasticizer is added that is not phthalate-based.

PLA resin is a thermoplastic polyester of lactide or lactic acid, and may be prepared by polymerizing lactic acid produced by fermenting starch extracted from renewable plant resources such as corn and potato. These PLA resins are environmentally friendly substances that can reduce the emission of environmentally harmful substances such as CO ₂ as compared with petroleum-based materials such as polyvinyl chloride (PVC) during use or disposal, .

On the other hand, PLA resin to be applied to the present invention, as described above, can be produced by polymerizing lactic acid or lactide, if necessary, glycol compounds, such as lactic acid or lactide and ethylene glycol or propylene glycol, ethanedio Hydroxycarboxylic acids such as dicarboxylic acid such as acid (ethanedioic acid) or terephthalic acid, glycolic acid or 2-hydroxybenzoic acid; Alternatively, it may be prepared by copolymerizing with a suitable monomer such as lactones such as caprolactone or propiolactone.

The PLA resin can be divided into a crystalline PLA (c-PLA) resin and an amorphous PLA (a-PLA) resin. At this time, in the case of the crystalline PLA resin, it is preferable to use an amorphous PLA resin because a bleeding phenomenon in which the plasticizer flows out to the sheet surface may occur. When an amorphous PLA resin is used, there is an advantage that a compatibilizer which is essentially added to prevent bleeding phenomenon is not added. When an amorphous PLA resin is used, it is most preferable to use a 100% amorphous PLA resin as the PLA resin, and a PLA resin in which crystalline and amorphous coexist can be used, if necessary.

In the present invention, an environmentally friendly nonphthalate plasticizer is added to the PLA resin.

The plasticizer softens the PLA resin to increase thermoplasticity, thereby facilitating molding at an appropriate processing temperature, and also serves to improve impact resistance. Such plasticizers include one or more of citric acid esters or acetyl citric acid esters, which are environmentally friendly plasticizers, which are not phthalate-based. It may be composed of three alcohol molecules to be combined. Specific examples include ATBC (acetyl tributyl citrate), TBC (tributyl citrate) and the like.

The plasticizer is preferably added in an amount ratio of 5 to 100 parts by weight based on 100 parts by weight of the PLA resin. When the plasticizer is added in an amount of less than 5 parts by weight based on 100 parts by weight of the PLA resin, the hardness of the PLA resin may be increased, and the workability may be reduced. When the amount of the plasticizer is added in an amount exceeding 100 parts by weight, the plasticity and flexibility are excessive but excessive. The use of the plasticizer may cause a bleeding phenomenon in which the plasticizer flows out to the flooring surface, thereby deteriorating the flooring properties.

The flooring may include a surface layer positioned on the surface side and a back layer 140 positioned on the bottom side, such as the transparent layer 120 illustrated in FIG. 1, and at least one layer of the surface layer 120 and the back layer 120 may be formed. The PLA resin may include a plasticizer.

The printed layer 130 shown in FIG. 1 is a layer on which a printed pattern is formed. In the case of the printed layer 130, the intermediate layer located between the transparent layer 120 on the front side and the back layer 140 on the back side is not strictly the surface layer and the back layer, but the printed layer may include PLA resin and plasticizer. Can be.

In addition, the flooring material may include a surface treatment layer such as a UV curable type, a polyurethane type, a wax type, and the like formed on the surface layer, such as the surface treatment layer 110 shown in FIG. At least one layer may include the PLA resin and a plasticizer.

Meanwhile, the PLA flooring material having excellent natural texture effect according to the present invention may be applied to a chip through type flooring material or a chip inlayed flooring material.

That is, the flooring material may be a chip through type flooring material including a chip through layer, and in this case, the chip through layer may include a PLA resin and a plasticizer.

In addition, the flooring material may be a chip inlay type flooring material including a chip inlaid layer, a glass fiber impregnation layer, and a backing layer from above, and at least one layer of the chip inlaying layer and the backing layer may be formed of PLA resin. And plasticizers.

The chip inlaid layer and the chip through layer may be formed in the following form, for example.

First, the chip inlaid layer may be prepared by processing a PLA resin, a plasticizer, and other additives such as wood powder into a sheet-like molded body, and then grinding the chip to form a chip, and then arranging and rolling the chip.

In addition, when a wood chip such as a wood chip is applied, the chip inlay deucheung layer may be prepared by processing such a wood chip into a sheet-like molded body by a calendering method by adding the wood chip to a raw material containing a PLA resin and a plasticizer.

The chip inlaid layer is applied when the chip is included in one layer when the flooring is composed of a plurality of layers, and the chip through layer is applied when the flooring is composed of one layer of the chip except for the surface treatment layer. Of course, the chip through layer may be in a form in which chips are formed from the top to the bottom of the flooring material, including the case where two or more chip layers including chips are thermally compressed or the like.

As described above, the PLA resin applied to the general lamination type, chip through type, and chip inlaid type may further include an acrylic copolymer, a lubricant, a hydrolysis agent, and the like.

The acrylic copolymer serves as a processing aid or a melt strength enhancer. Since the PLA resin does not have good melt strength or heat resistance in itself, the PLA resin may be added to reinforce the melt strength of the PLA resin to be processed by calendering or pressing.

The acrylic copolymer is preferably added in a proportion of 0.1 to 20 parts by weight based on 100 parts by weight of the PLA resin. When the content of the acrylic copolymer is less than 0.1 parts by weight, the improvement of the melting efficiency and the melt strength of the PLA resin is insufficient, and when the content of the acrylic copolymer exceeds 20 parts by weight with other materials constituting each layer constituting the flooring material. Due to compatibility problems, the overall physical properties of each layer may be reduced.

Lubricant serves to prevent the PLA resin from adhering to the calender roll or press during processing of calendering, pressing, and the like. Glidants that play this role can be higher fatty acids, specifically stearic acid.

The lubricant is preferably added in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the PLA resin. If the lubricant is less than 0.01 parts by weight relative to 100 parts by weight of the PLA resin, the lubricant may not be added. On the contrary, if the lubricant is more than 10 parts by weight, the impact resistance, heat resistance, glossiness, etc. of the PLA resin may be degraded.

The hydrolysis agent serves to impart the water resistance of the flooring material by inhibiting the hydrolysis reaction. Such a hydrolysis agent may be used without limitation so long as it is usually used as a hydrolysis agent such as polycarbodiimide, carbodiimide, oxazoline, and the like.

The hydrolysis agent is preferably added in an amount ratio of 10 parts by weight or less based on 100 parts by weight of the PLA resin. When the hydrolysis agent is added in a large amount, the water resistance may be improved, but when the hydrolysis agent is added in excess of 10 parts by weight relative to 100 parts by weight of the PLA resin, molding processability may be deteriorated.

In addition to the plasticizer and the above additives, the PLA resin further includes at least one inorganic reinforcing agent, calcium carbonate (CaCO ₃ ), white pigment titanium dioxide (TiO ₂ ), and wood flour or rosin, which may represent the texture of natural wood. Can be.

In this case, the calcium carbonate is preferably added in an amount of 1,000 parts by weight or less with respect to 100 parts by weight of the PLA resin, and titanium dioxide is preferably added in an amount of 50 parts by weight or less relative to 100 parts by weight of the PLA resin. When calcium carbonate or titanium dioxide is used in excess of the above range, the binding force of other components may be lowered, thereby decreasing workability.

In addition, the wood powder is preferably added to 200 parts by weight or less with respect to 100 parts by weight of the PLA resin, the rosin is preferably 20 parts by weight or less based on 100 parts by weight of PLA resin. When these wood flour or rosin is added in excess of the above range, there is a problem in that moldability becomes difficult without any natural texture effect.

In the present invention, a method for producing a layer containing a PLA resin by applying a calendering method, etc. is not particularly limited, and, for example, after mixing and kneading the raw materials including the above-described PLA resin and a plasticizer, a desired sheet It may be produced through a process of calendering molding into a shape.

The mixing and kneading of the raw materials can be performed, for example, by using a super mixer, an extruder, a kneader, a double or triple roll, or the like in the form of a liquid or a powdery raw material. Further, in the mixing and kneading step of the raw materials, the blended raw materials are kneaded at a temperature of about 120 to 200 DEG C using a Banbury mixer or the like, and the kneaded raw materials are heated to about 120 to 200 DEG C The mixing and kneading steps may be repeatedly carried out in multiple stages as in the case of primary and secondary mixing using a two-roll mill or the like at a temperature of 50 to 100 ° C.

On the other hand, the method of producing the sheet-like layer by applying the mixed raw materials as described above to the calendering method is also not particularly limited, and can be produced using, for example, a conventional apparatus such as an inverted L four-roll roll calender. .

The car rendering processing conditions described above can be appropriately selected in consideration of the composition of the resin composition to be used, and the car rendering processing can be performed within a processing temperature range of about 120 to 200 ° C.

Manufacturing example

Below, the preferable manufacture example of this invention is described. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

100 parts by weight of the PLA resin, 25 parts by weight of ATBC, 10 parts by weight of the acrylic copolymer, 5 parts by weight of stearic acid, and 3 parts by weight of carbodiimide were kneaded first using an extruder, and then kneaded at 140 ° C. with a half-barrier mixer, Primary and secondary mixing were performed using a 140 roll dual roll. Then, the produced raw material was calendered at the temperature of 130 degreeC, and the sheet | seat sample for flooring materials having a thickness of about 0.5 mm was manufactured.

The sheet sample was measured to be approximately 8.3 kgcm / cm impact strength measured by the ASTM D256 method. When not added as a plasticizer, the impact resistance of the PLA sheet is only about 1.2 kgcm / cm, the impact strength of the preparation is considerably high, which means that the plasticity of the preparation is excellent.

On the other hand, the impact resistance of the prepared PLA sheet was 8.5 kgcm / cm when ATBC 120 parts by weight as a plasticizer, but a bleeding phenomenon occurred on the sheet surface.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. . Accordingly, the true scope of the present invention should be determined by the following claims.

110: surface treatment layer
120: transparent layer
130: Printed layer
140: back layer

Claims (14)

In flooring formed of one or more layers,
At least one layer of the flooring material comprises a PLA resin and a non-phthalate-based eco-friendly plasticizer, the PLA resin comprises an amorphous PLA resin,
The non-phthalate eco-friendly plasticizer includes at least one of citric acid ester or acetyl citric acid ester, and the ester is one selected from citric acid molecule, ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol Eco-friendly PLA flooring with excellent plasticity, characterized in that consisting of alcohol molecules.
delete The method of claim 1,
The plasticizer is excellent eco-friendly PLA flooring material, characterized in that added to the content ratio of 5 to 100 parts by weight with respect to 100 parts by weight of the PLA resin.
The method of claim 1,
The PLA resin has a plasticity, characterized in that it further comprises one or more additives of 0.1 to 20 parts by weight of the acrylic copolymer, 0.01 to 10 parts by weight of lubricant, 10 parts by weight or less of the hydrolysis agent, based on 100 parts by weight of the PLA resin. Excellent eco-friendly PLA flooring.
5. The method of claim 4,
The PLA resin further comprises one or more additives of less than 1,000 parts by weight of calcium carbonate, 50 parts by weight of titanium dioxide, 200 parts by weight of wood powder and 20 parts by weight of rosin, based on 100 parts by weight of the PLA resin. Eco-friendly PLA flooring with excellent plasticity.
The method of claim 1,
The flooring material includes a surface treatment layer and a back surface layer,
Eco-friendly PLA flooring material having excellent plasticity, characterized in that at least one layer of the surface treatment layer and the back layer comprises the PLA resin and the plasticizer.
The method of claim 1,
The flooring material includes a surface treatment layer,
At least one layer except for the surface treatment layer is an eco-friendly PLA flooring material having excellent plasticity, characterized in that containing the PLA resin and the plasticizer.
In a flooring material comprising a chip through layer,
The chip through layer comprises a PLA resin and a non-phthalate-based eco-friendly plasticizer, the PLA resin includes an amorphous PLA resin,
The non-phthalate plasticizer includes at least one of citric acid ester or acetyl citric acid ester, and the ester is one citric acid molecule and three alcohols arbitrarily selected and combined from ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol and octyl alcohol. Eco-friendly PLA flooring with excellent plasticity, characterized in that consisting of molecules.
delete 9. The method of claim 8,
The plasticizer is excellent eco-friendly PLA flooring material, characterized in that added to the content ratio of 5 to 100 parts by weight with respect to 100 parts by weight of the PLA resin.
In the flooring comprising a chip inlay layer, a glass fiber impregnation layer and a back layer from above,
At least one layer of the chip inlay deucheung and the back layer comprises a PLA resin and non-phthalate-based plasticizer, the PLA resin comprises an amorphous PLA resin,
The non-phthalate plasticizer includes at least one of citric acid ester or acetyl citric acid ester, and the ester is one citric acid molecule and three alcohols arbitrarily selected and combined from ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol and octyl alcohol. Eco-friendly PLA flooring with excellent plasticity, characterized in that consisting of molecules.
delete 12. The method of claim 11,
The plasticizer is excellent eco-friendly PLA flooring material, characterized in that added to the content ratio of 5 to 100 parts by weight with respect to 100 parts by weight of the PLA resin.
delete

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